CN108840993A - D-A-D' asymmetric structure polymeric membrane PEWT as well as preparation method and application thereof - Google Patents
D-A-D' asymmetric structure polymeric membrane PEWT as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN108840993A CN108840993A CN201810491811.4A CN201810491811A CN108840993A CN 108840993 A CN108840993 A CN 108840993A CN 201810491811 A CN201810491811 A CN 201810491811A CN 108840993 A CN108840993 A CN 108840993A
- Authority
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- China
- Prior art keywords
- pewt
- polymeric membrane
- electrode
- unsymmetric structure
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 73
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920006254 polymer film Polymers 0.000 claims abstract description 22
- 230000009471 action Effects 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 124
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 93
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 33
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical group [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 239000001103 potassium chloride Substances 0.000 claims description 14
- 235000011164 potassium chloride Nutrition 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910000080 stannane Inorganic materials 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 10
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 1- butyl -3- methyl imidazolium tetrafluoroborate Chemical compound 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 14
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229960000935 dehydrated alcohol Drugs 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 229920000547 conjugated polymer Polymers 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920005597 polymer membrane Polymers 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 5
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a DAD' asymmetric structure polymeric membrane PEWT as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: under the action of an electron donating group, 2, 7-dibromo-9 fluorenone shown in the formula 1 is subjected to coupling reaction to form an asymmetric DAD 'structural monomer, and polymerization reaction is carried out at room temperature by adopting a cyclic voltammetry polymerization method to obtain an asymmetric DAD' structural polymer film deposited on a working electrode. The method provided by the invention is simple to operate, the monomer yield and the purity of the polymer film are higher, the prepared product has more prominent multicolor display and excellent electrochromic performance, and the material can be applied to electrochromic devices.
Description
Technical field
The present invention relates to D-A-D ' (donor-acceptor-donor ') unsymmetric structure polymeric membrane PEWT that kind has multicolor displaying
And preparation method thereof described in the polymeric membrane PEWT of D-A-D ' unsymmetric structure can be applied to prepare electrochromic device.
Technical background
Since the electrochromism of auto polymerization object (PEC) material is found, because it has knot compared to inorganic electrochromic material
The advantages that structure is easily modified, and coloration efficiency is high, optical contrast is high and fast response time, it is considered to be next-generation EC material
One of developing direction.Currently, the method for realizing electrochromic polymeric compounds multicolor displaying by MOLECULE DESIGN or modification mainly has,
Copolymerization between the design and different molecular of donor-receiver (D-A) molecular structure, wherein copolymerization product is not known because of molecular structure
Property, it is unfavorable for the control to quality in the mechanism study of electrochromic material discoloration and actual production.
And D-A structure then can Effective Regulation molecule energy band, adjust the electrochromic property of polymer.Nowadays, there are many
D-A structure class conjugated polymer is reported, such as with diazosulfide, benzo quinoline oh, thiophen pyrazine, Fluorenone and its derivative be
The D-A structure copolymer of receptor.But the application of the understanding and material to its mechanism is still limited, understands conjugated polymer to be deep
The molecular structure of electrochromic material and the relationship of its photoelectric properties, solve existing D-A-D asymmetric conjugate polymer P EWE (in fluorenes
Ketone both ends are introduced into the Molecularly Imprinted Polymer of identical 3,4-rthylene dioxythiophene (EDOT)) oxidizing potential in electrochromic property
Single, discoloration shows the problems such as single optical contrast is general.It is asymmetric total that we devise a kind of D-A-D ' based on Fluorenone
Conjugated polymer PEWT (introduces 3,4-rthylene dioxythiophene (EDOT) and the not isoplastic molecule aggregation of triphenylamine at Fluorenone both ends
Object), and study molecular structure its color is shown, the influence of state of aggregation pattern, the performances such as optical contrast, and find its compared with
The electrochromic property of PEWE is more excellent.
Summary of the invention
There are oxidizing potentials to solve existing D-A-D asymmetric conjugate polymer P EWE, and single, discoloration shows single optics pair
The problems such as more general than degree, the object of the present invention is to provide a kind of D-A-D ' dissymmetrical structure polymer P EWT, and finding should
It is more abundant that polymer not only makes electrochromic display, but also under certain wavelength, optical contrast with higher.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of D-A-D ' unsymmetric structure polymeric membrane PEWT, D-A-D ' the unsymmetric structure polymeric membrane PEWT are specifically pressed
It is prepared according to following method：
(1) -9 Fluorenone of 2,7-, bis- bromo shown in formula 1 and 4- (diphenyl amido) phenyl boric acid, four (three) phenyl phosphorus palladiums is mixed
It closes, under the action of alkaline matter A, is dissolved in organic solvent A in the case where nitrogen is protected, reacts 8-12 at a reflux temperature
Hour, reaction mixture B is obtained, it is post-treated to obtain product 2- triphenylamine -7- bromo -9-Fluorenone shown in formula 2；The formula 1
Shown in the ratio between -9 Fluorenone of 2,7-, bis- bromo and 4- (diphenyl amido) phenyl boric acid, the amount of substance of four (two) phenyl phosphorus palladiums be 1:
0.5~1: 0.001~0.005；The alkaline matter A is added in form of an aqueous solutions, and the additional amount of the water is with just molten
It solves subject to alkaline matter A；The additional amount of the alkaline matter A is calculated as 2~4mol/L with the volume of the organic solvent A；
(2) by 2- triphenylamine -7- bromo -9-Fluorenone shown in formula 2, (2,3- dihydro-thiophenes are simultaneously [3,4-b]-with tributyl
[Isosorbide-5-Nitrae] dioxin -5- base) stannane, bi triphenyl phosphorus palladium chloride, it is molten in the case where nitrogen is protected under the action of alkaline matter B
Solution reacts 24-36 hours at a reflux temperature in organic solvent B, obtains reaction mixture C, post-treated to obtain shown in formula 3
D-A-D ' unsymmetric structure monomer EWT；2- triphenylamine -7- bromo -9- the Fluorenone and tributyl (2,3- dihydro-thiophenes
And [3,4-b]-[Isosorbide-5-Nitrae] dioxin -5- base) stannane, bi triphenyl phosphorus palladium chloride the ratio between the amount of substance be 1: 1~2:
0.001~0.005；The alkaline matter B is added in form of an aqueous solutions, and the additional amount of the water to dissolve basic species just
Subject to matter B；The additional amount of the organic solvent A is with the meter of the substance of -9 Fluorenone of 2,7-, bis- bromo shown in the formula 1
For 10~100mL/mmol；The additional amount of the alkaline matter B is calculated as 2~4mol/L with the volume of the organic solvent B；
The additional amount of the organic solvent B is calculated as with the amount of 2- triphenylamine -7- bromo -9-Fluorenone substance shown in the formula 2
10~100mL/mmol；
(3) D-A-D ' unsymmetric structure monomer EWT obtained by step (3), support electrolyte are dissolved in electroanalysis solvent and are obtained
Electrolyte, in three-electrode cell, using cyclic voltammetric anodic oxidation polymerization method, in polymerization voltage range in 0~1.6V
Vs.Ag/AgCl carries out deposition reaction, after fully reacting, obtains being deposited on work under conditions of polymerisation loop circle number is 2~32
Make the thin polymer film on electrode, through organic solvent cleaning, is dried to obtain thin polymer film PEWT shown in formula 4；The branch
Support electrolyte is ammonium salt, lithium salts or 1- butyl -3- methyl imidazolium tetrafluoroborate；It is 1 that the electrolytic cell solvent, which is volume ratio:
0.1~10 acetonitrile (chromatographic grade) and the mixed solvent of methane dioxide (chromatographic grade)；D-A-D ' the unsymmetric structure monomer
EWT supports the additional amount of electrolyte in terms of the volume beam of the electroanalysis solvent, D-A-D ' the unsymmetric structure list
Initial final concentration of 0.1~10mmol/L electroanalysis solvent of body EWT, initial final concentration of the 0.01 of the supporting electrolyte
~1mol/L electroanalysis solvent；
The three-electrode system is made of electrolytic cell, working electrode, auxiliary electrode and reference electrode, the work electricity
Extremely perhaps the PET conductive film electrode auxiliary electrode is platinum electrode or platinum by indium tin oxide-coated glass (ITO), FTO
Carbon electrode, it with the potassium chloride solution of 3mol/L is that the first liquid connects that the reference electrode, which is Ag/AgCl, with the electrolysis
Liquid is that the second liquid connects；
Further, -9 Fluorenone of 2,7-, bis- bromo shown in the formula 1 can be prepared as follows：
Using Fluorenone as raw material, iodine be catalyst, water is solvent, and bromine is added dropwise while stirring, and 100 DEG C of bromos are anti-
It answers 4-6 hours, obtains reaction mixture A, filtered after system is cooling, gained filter cake is successively with being saturated solution of sodium bisulfite, go
Ion water washing obtains -9 Fluorenone of 2,7-, bis- bromo shown in formula 1 after dry；The iodine and Fluorenone, bromine substance amount it
Than being 1: 150: 300~450；The additional amount of the water is calculated as 1.5~2ml/mmol with the amount of the substance of the Fluorenone.
Further, in step (1), the alkaline matter A is sodium carbonate, sodium bicarbonate or potassium carbonate etc., preferably carbon
Sour potassium.
Further, in step (1), the organic solvent A is that tetrahydrofuran is mixed with what toluene mixed in any proportion
The mixed liquor of tetrahydrofuran and toluene that bonding solvent, preferably volume ratio are 1: 0.5~2.
Further, in step (1), the last handling process of gained reaction mixture B is：After reaction, it is reacted to gained
Methylene chloride is added in mixed liquid B to be extracted, merging organic phase is simultaneously dry with anhydrous magnesium sulfate, and revolving mixes sample, with volume ratio
It is that mobile phase composition is obtained through chromatography for 1: 0.5-1.5 petroleum ether (PE) and the mixed solvent of methylene chloride (DCM)
2- triphenylamine -7- bromo -9-Fluorenone shown in formula 2.
Further, in step (2), the alkaline matter B is sodium carbonate, sodium bicarbonate or potassium carbonate etc., preferably carbon
Sour potassium.
Further, in step (2), the organic solvent B is tetrahydrofuran and toluene mixing of connecing that arbitrary proportion mixes
The volume ratio of bonding solvent, preferably tetrahydrofuran and toluene is 1: 0.5~2.
Further, in step (2), the last handling process of gained reaction mixture C is：After reaction, anti-to gained
It answers the mix reagent that deionized water and methylene chloride are added in mixed liquor C to be extracted, merges organic phase and with anhydrous thin acid magnesium
Dry, revolving mixes sample, the mixed solvent of the petroleum ether (PE) and methylene chloride (DCM) that be 1: 0.5-1.5 with volume ratio is to flow
Phase component obtains D-A-D ' unsymmetric structure monomer EWT shown in formula 3 through chromatography；
Further, in step (3), the ammonium salt is tetrabutylammonium perchlorate (TBAP) or tetrabutyl ammonium hexafluorophosphate
(TBAPF6)。
Further, in step (3), the reason salt is lithium hexafluoro phosphate, LiBF4 or trifluoromethyl sulfonic acid lithium etc..
Further, in step (3), it is described for cleaning organic solvent be volume ratio be 1: 0.1~10 acetonitrile with
The mixed solvent of methylene chloride.
In step (3), the working electrode is successively 0.1% sodium hydroxide solution, dehydrated alcohol, third in mass fraction
Supersound washing is carried out in ketone, toluene, dehydrated alcohol, toluene and acetone, preferably ultrasonic time is respectively 15min.
Further, in step (3), the auxiliary electrode needs are processed by shot blasting.
Thin polymer film of the present invention with a thickness of 30~630nm.
The structure of monomer of the present invention is by nuclear magnetic resonance spectroscopy (NMR) and mass spectral characteristi；Have to the characterization of polymer
Scanning electron microscope (SEM), ultraviolet-visible spectrum (UV), electrochemical workstation.By the NMR and mass spectrum of monomer, it was confirmed that single
The formation of body；By the combination of ultraviolet-visible spectrum (UV) and electrochemical workstation, its purple under different voltages has been obtained
Outside-visible spectrum absorbs and the contrast under different spectrum, response time, and then directly confirms D-A-D ' unsymmetric structure one
The color for improving electrochromic material under fixed condition shows, optical contrast or response time；It is right by scanning electron microscope (SEM)
The pattern of resulting polymers film is characterized, it was demonstrated that D-A-D ' unsymmetric structure is relative to D-A-D symmetrical structure to electroluminescent change
The state of aggregation pattern of color material is brought greater impact.
Compared with prior art, the beneficial effects of the present invention are：
(1) polymerization process for preparing of D-A-D ' dissymmetrical structure material is easy in the present invention, does not need harsh reaction item
Part can be carried out operating at room temperature, and without complicated purification process, product purity is higher, and preparation energy consumption is lower, and saves
The moulding process of material, therefore this method is easy to operate, cost is relatively low, easily controllable structure (size, thickness and character etc.),
Be conducive to commercial applications.
(3) compared to D-A-D symmetrical structure PEWE, what electrochemistry was prepared in the present invention is film material, the shape of film
Looks are more fluffy, and after stability test, discovery PEWT film pattern variation is little；Pass through the actual assembled to the polymeric membrane, hair
Now the polymerization membrane rigidity is larger, and it is more crisp to show as film, is easily destroyed, and need to improve in probing into from now on it.
(4) in the present invention, by the electrochemistry cyclic voltammetry curve of polymeric membrane it is found that D-A-D ' dissymmetrical structure conjugated polymers
The more redox sites of object have more metastable states.
(5) the D-A-D ' dissymmetrical structure conjugated polymer PEWT has more redox peaks and richer color
Display.And as the raising of voltage, PEWT have more colors, when being in middle condition, which is shown as BurlyWood；With
The raising of voltage, the film slowly become blue, when reaching 0.9V to voltage, be shown as bright rock grey；Then, voltage is slowly brought up to
1.4V is shown as mine purple.And in PEWE under condition it is solarization color, it is gray purple under oxidation state, color shows more single.
(6) it is measured by film thickness of the Dektak-XT surface profiler under several to material difference polymerization circle, finds D-A-
D ' unsymmetric structure material PEWT polymerize what circle number increased with cyclic voltammetric compared to D-A-D symmetrical structure material PEWE, film thickness
Faster, which may exist certain related with the solubility and membrane structure of material monomer, need to continue to explore from now on.
(7) under film thickness, at 1100nm, contrast rises to the 48.8% of PEWT by the 313% of PEWE；It is right at 650nm
It is increased to the 26.7% of PEWT by the 11.4% of PEWE than degree, relative to D-A-D symmetrical structure polymeric membrane PSWS, triphenylamine base
The introducing of group has significantly alterred it in visible and near infrared region optical contrast.
Detailed description of the invention
Fig. 1 schemes for the SEM of thin polymer film obtained in comparative example；
Fig. 2 is the cyclic voltammogram of monomer polymerization in comparative example；
Fig. 3 is the cyclic voltammogram of polymeric membrane in comparative example；
Fig. 4 schemes for the SEM of thin polymer film obtained in embodiment 1；
Fig. 5 is the cyclic voltammogram of monomer polymerization in embodiment 1；
Fig. 6 is the cyclic voltammogram of polymeric membrane in embodiment 1；
Fig. 7 is the measurement chart of thin polymer film film thickness in comparative example and embodiment (using Dektak-XT surface profile
Instrument)；
Fig. 8 is the schematic diagram of thin polymer film PEWE and PEWT optical contrast under identical film thickness；
Specific embodiment
Below by specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.The present invention prepares thin polymer film using cyclic voltammetric polymerization, and the instrument used in whole preparation process is electrochemistry work
It stands (CHI660E, Shanghai Chen Hua instrument company) and three-electrode system.
In embodiment, the voltage range when PEWT polymeric membrane photoelectric properties are tested is 0~1.6V vs.Ag/
AgCl。
Prepare -9 Fluorenone of 2,7-, bis- bromo first, in 100mL cleaning flask middle addition 4g Fluorenone, 35mL aqueous solvent and
0.015g iodine catalyst, and 3mL bromine is added dropwise under stiring, 100 degree are heating 6 hours lower, filter after system is cooling, gained filter cake
It is successively washed with saturation solution of sodium bisulfite, deionized water, obtains yellow solid target product after dry.
In addition, need to prepare tributyl (2,3- dihydro-thiophenes simultaneously [3,4-b]-[Isosorbide-5-Nitrae] dioxin -5- base) stannane in experiment,
Specific step is as follows：At -78 DEG C, n-BuLi (1.6M) is slowly added dropwise, and stir 0.5h, then, temperature is increased to -40
DEG C, positive tributyltin chloride (18.8mmol, 6.12g) is slowly added dropwise, and react 8h at room temperature, separate up to tributyl (2,
3- dihydro-thiophene simultaneously [3,4-b]-[Isosorbide-5-Nitrae] dioxin -5- base) stannane.
Comparative example
(1) preparation of monomer EWE
By -9 Fluorenone (3mmol, 1.014g) of 2,7-, bis- bromo, tributyl (2,3- dihydro-thiophenes simultaneously [3,4-b]-[Isosorbide-5-Nitrae] two
Dislike English -5- base) and stannane (7mmol, 3.0248 g), potassium carbonate (3mmol, 1.3821g) and bi triphenyl phosphorus palladium chloride
(0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and is added 2ml's
Deionized water flows back 24 hours in nitrogen atmosphere, after system is cooling, is extracted with deionized water and methylene chloride mix reagent
It takes, gained is organic to be added to anhydrous thin sour magnesium drying, and revolving mixes sample later, selects corresponding mobile phase (PE: DCM=1: 1.5)
Column was chromatographed, monomer (EWE) is finally obtained.1H NMR (500MHz, CDCl3) δ 8.07 (d, J=1.6Hz, 1H), 7.82 (dd,
J=7.9,1.7Hz, 1H), 7.78 (d, J=1.8Hz, 1H), 7.61 (dd, J=7.9,1.8Hz, 1H), 7.49 (d, J=
7.9Hz, 1H), 7.39 (d, J=7.9Hz, 1H), 6.36 (s, 1H), 4.38-4.34 (m, 2H), 4.30-4.25 (m, 3H)
.MALDI-TOF-MS(M)(m/z)：461.1[M+H]+.
(2) preparation of polymer (PEWE) material
EWE monomer (1mmol, 0.0046g), tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in 7ml methylene chloride
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte concentration is the mixed of 0.1mol/L
Solution is closed as electrolyte.Three-electrode cell system is selected, (is successively existed using indium tin electro-conductive glass (ITO) as working electrode
Supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, interior ketone, toluene, dehydrated alcohol, toluene and acetone), to throw
The platinum filament that light is crossed is reference electrode (Ag/ as auxiliary electrode (platinum filament length 4cm), using biliquid direct type silver/silver chloride electrode
The potassium chloride solution of AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).In room
Under warm (25 DEG C), thin polymer film, cyclic voltammetric are prepared using cyclic voltammetric anodic oxidation polymerization method by electrochemical workstation
Method refers to one linear ramp of application on the electrode, is scanned with constant pace of change, when the termination for reaching a certain setting
When voltage, then reversely it is returned to the starting voltage of former setting.Therefore, the starting voltage 0v of the monomer polymerization is set first, is terminated
Voltage 1.6v and sweep speed 0.1v/s, and polymerisation loop circle number is set as 26 (obtained polymeric film thicknesses are 630nm), start
Electrochemical workstation；Such as Fig. 2, which is the cyclic voltammetric polymerization curve of monomer, and by Tu Kejia, the oxidizing potential of monomer is
0.71v shows that polymerization current potential is lower, and energy consumption is less, is conducive to actual production application.It is conductive to polymerize power cut-off electrode ITO
Glass surface deposited one layer of polymeric film, be cleaned with methylene chloride, and the work of surface deposited polymer membrane is obtained after dry
Make electrode, as shown in Figure 1, seeing that polymeric film surface state of aggregation is more homogeneous close by electronic scanner microscope, through 500
After a cyclic voltammetric stability test, polymeric membrane forms more fluff structure, shows that polymerization membrane stability is not satisfactory.
(3) polymer (PEWE) electrochemical property test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in the mixed solution of 6ml methylene chloride and 4ml acetonitrile, is matched
The electrolyte solution that concentration is 0.1mol/L is made, selects three-electrode cell system, it is electric using polymeric membrane PEWE as work
Reference electricity is done using biliquid direct type silver/silver chloride electrode using polished platinum filament as auxiliary electrode (platinum filament length 4cm) in pole
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains is as the second liquid for pole
It connects).At room temperature, the cyclic voltammetry curve of the polymeric membrane is tested, it has been found that the polymeric membrane only has a pair of of redox peaks,
And color change is single, under middle condition, is shown as solarization color, with the raising of voltage, oxidation state becomes gray purple.
Embodiment 1
(1) preparation of monomer EWT
First by -9 Fluorenone (3mmol, 1.044g) of 2,7-, bis- bromo, 4- (diphenyl amido) phenyl boric acid (1.5mmol,
0.438g), the feelings that potassium carbonate (2mmol, 0.2764g) and four (three) phenyl phosphorus palladiums (0.0025mmol, 0.0311g) are protected in nitrogen
It is dissolved under condition in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and the deionized water of 2ml is added, flowed back 8
Hour, it after system is cooling, is extracted with deionized water and methylene chloride mix reagent, the organic anhydrous magnesium sulfate that is added to of gained is done
Dry, revolving mixes sample later, selects corresponding mobile phase to chromatograph column, finally obtains 2- triphenylamine -7- bromo -9- Fluorenone monomer；
Later, by 2- triphenylamine -7- bromo -9-Fluorenone monomer (3mmol, 1.503g), tributyl, (2,3- dihydro-thiophenes are simultaneously [3,4-b] -
[Isosorbide-5-Nitrae] dioxin -5- base) stannane (3mmol, 1.2963g), potassium carbonate (2mmol, 0.2764g) and bi triphenyl phosphorus dichloride
Palladium (0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20mL) and toluene (30mL), and 2ml is added
Deionized water, flow back in nitrogen atmosphere 24 hours, after system is cooling, with deionized water and methylene chloride mix reagent
Extraction, gained is organic to be added to that anhydrous magnesium sulfate is dry, and revolving mixes sample later, select corresponding mobile phase (PE: DCM=1:
1.5) column was chromatographed to get monomer (EWT).1H NMR (500MHz, DMSO) δ 8.08 (d, J=1.4Hz, 1H), 7.92 (d, J
=1.5Hz, 1H), 7.82 (dd, J=7.9,1.7Hz, 1H), 7.73 (dd, J=7.8,1.8Hz, 1H), 7.51 (d, J=3.9
Hz, 1H), 7.50 (d, J=4.1Hz, 1H), 7.39 (dd, J=3.6,1.0Hz, 1H), 7.32 (dd, J=5.1,1.0Hz, 1H),
7.11 (dd, J=5.1,3.6 Hz, 1H), 6.35 (s, 1H), 4.40-4.34 (m, 2H), 4.30-4.24 (m, 2H)) MALDI-
TOF-MS(M)(m/z)：564.1[M+H]+.
(2) preparation of polymer (PEWT) material
EWT monomer (1mmol, 0.00563g), tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in 7ml methylene chloride
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte TBAP concentration is 0.1mol/L
Mixed solution as electrolyte.Select three-electrode cell system, using indium tin electro-conductive glass (ITO) as working electrode (according to
The secondary supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, acetone, toluene, dehydrated alcohol, toluene and acetone),
Using polished platinum filament as auxiliary electrode (platinum filament length 4cm), reference electrode is done using biliquid direct type silver/silver chloride electrode
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).
Under room temperature (25 DEG C), thin polymer film is prepared using cyclic voltammetric anodic oxidation polymerization method, sets the monomer polymerization first
Starting voltage 0v, final voltage 1.6v and sweep speed 0.1v/s, and set polymerisation loop circle number and (obtain polymeric film thicknesses as 16
For 630nm), start the working procedure of electrochemical workstation.Such as Fig. 5, which is the cyclic voltammetric polymerization curve of monomer, by
Figure is it is found that the oxidizing potential of monomer is 1.1v and 1.47v, and monomer molecule has excellent polymerization film formation ability, thus may be used
Know that there are more oxidation-reduction potentials compared to EWE, structures alone EWT.It polymerize power cut-off electrode ITO electro-conductive glass
Surface deposited one layer of polymeric film, be cleaned with methylene chloride, and the work electricity of surface deposited polymer membrane is obtained after dry
Pole, as shown in Figure 4, polymer is more loose relatively above on the surface of thin polymer film, but after 500 circulations, pattern
Variation is smaller, illustrates that polymeric membrane is relatively stable.
(3) polymer (PEWT) electrochemical property test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in the mixed solution of 6ml methylene chloride and 4ml acetonitrile, is matched
The electrolyte solution that concentration is 0.1mol/L is made, selects three-electrode cell system, it is electric using polymeric membrane PEWT as work
Reference electricity is done using biliquid direct type silver/silver chloride electrode using polished platinum filament as auxiliary electrode (platinum filament length 4cm) in pole
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains is as the second liquid for pole
It connects).At room temperature, test the cyclic voltammetry curve of the polymeric membrane, i.e., in the case where polymerizeing 0~1.6V of voltage range vs.Ag/AgCl,
To the working electrode containing polymeric membrane with rate loop voltammetric scan one week of 0.1v/s, it will be appreciated from fig. 6 that the D-A-D ' is asymmetric
There are structure conjugated polymer PEWT more redox peaks and richer color to show when in middle condition, the material
It is shown as BurlyWood；With the raising of voltage, which slowly becomes blue, when reaching 0.9V to voltage, is shown as bright rock grey；With
Afterwards, voltage is slowly brought up to 1.4V, is shown as mine purple.As Fig. 8 and with shown in table 1, under identical film thickness, at 1100nm, compare
Degree rises to the 48.8% of PEWT by the 313% of PEWE；At 650nm, contrast is increased to PEWT's by the 11.4% of PEWE
26.7%, relative to D-A-D symmetrical structure polymeric membrane PSWS, the introducing of trianilino group has significantly alterred it visible and close
The optical contrast of infrared region, specific spectrum dynamic parameters are as shown in table 1.
Table 1 is the spectrum dynamic performance of thin polymer film PEWE and PEWT in comparative example and embodiment 1
Embodiment 2
(1) preparation of monomer EWT
First by -9 Fluorenone (3mmol, 1.044g) of 2,7-, bis- bromo, 4- (diphenyl amido) phenyl boric acid (1.5mmol,
0.438g), the feelings that potassium carbonate (2mmol, 0.2764g) and four (three) phenyl phosphorus palladiums (0.0025mmol, 0.0311g) are protected in nitrogen
It is dissolved under condition in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and the deionized water of 2ml is added, flowed back 6
Hour, it after system is cooling, is extracted with deionized water and methylene chloride mix reagent, the organic anhydrous magnesium sulfate that is added to of gained is done
Dry, revolving mixes sample later, selects corresponding mobile phase to chromatograph column, finally obtains 2- triphenylamine -7- bromo -9- Fluorenone monomer；
Later, by 2- triphenylamine -7- bromo -9-Fluorenone monomer (3mmol, 1.503g), tributyl, (2,3- dihydro-thiophenes are simultaneously [3,4-b] -
[Isosorbide-5-Nitrae] dioxin -5- base) stannane (3mmol, 1.2963g), potassium carbonate (2mmol, 0.2764g) and bi triphenyl phosphorus dichloride
Palladium (0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20mL) and toluene (30mL), and 2ml is added
Deionized water, flow back in nitrogen atmosphere 36 hours, after system is cooling, with deionized water and methylene chloride mix reagent
Extraction, gained is organic to be added to that anhydrous thin sour magnesium is dry, and revolving mixes sample later, select corresponding mobile phase (PE: DCM=1:
1.5) column was chromatographed to get monomer (EWT).1H NMR (500MHz, DMSO) δ 8.08 (d, J=1.4Hz, 1H), 7.92 (d, J
=1.5Hz, 1H), 7.82 (dd, J=7.9,1.7Hz, 1H), 7.73 (dd, J=7.8,1.8Hz, 1H), 7.51 (d, J=3.9
Hz, 1H), 7.50 (d, J=4.1Hz, 1H), 7.39 (dd, J=3.6,1.0Hz, 1H), 7.32 (dd, J=5.1,1.0Hz, 1H),
7.11 (dd, J=5.1,3.6 Hz, 1H), 6.35 (s, 1H), 4.40-4.34 (m, 2H), 4.30-4.24 (m, 2H)) MALDI-
TOF-MS(M)(m/z)：564.1[M+H]+.
(2) preparation of polymer (PEWT) material
EWT monomer (1mmol, 0.00563g), tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in 7ml methylene chloride
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte TBAP concentration is 0.1mol/L
Mixed solution as electrolyte.Select three-electrode cell system, using indium tin electro-conductive glass (ITO) as working electrode (according to
The secondary supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, acetone, toluene, dehydrated alcohol, toluene and acetone),
Using polished platinum filament as auxiliary electrode (platinum filament length 4cm), reference electrode is done using biliquid direct type silver/silver chloride electrode
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).
Under room temperature (25 DEG C), thin polymer film is prepared using cyclic voltammetric anodic oxidation polymerization method, sets the monomer polymerization first
Starting voltage 0v, final voltage 1.6v and sweep speed 0.1v/s, and set polymerisation loop circle number and (obtain polymeric film thicknesses as 16
For 630nm), start the working procedure of electrochemical workstation.By the cyclic voltammetric polymerization curve of monomer it is found that the oxygen of monomer
Change current potential is 1.1v and 1.47v, and monomer molecule has excellent polymerization film formation ability, compared to EWE, structures alone EWT
With more oxidation-reduction potentials.Polymerization power cut-off electrode ITO conductive glass surface deposited one layer of polymeric film, use
Methylene chloride cleaning obtains the working electrode of surface deposited polymer membrane, is characterized by scanning electron microscope it is found that polymer after dry
Polymer is more loose relatively above on the surface of film, but after 500 circulations, pattern variation is smaller, illustrates polymeric membrane
It is relatively stable.
(3) polymer (PEWT) electrochemical property test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in the mixed solution of 6ml methylene chloride and 4ml acetonitrile, is matched
The electrolyte solution that concentration is 0.1mol/L is made, selects three-electrode cell system, it is electric using polymeric membrane PEWT as work
Reference electricity is done using biliquid direct type silver/silver chloride electrode using polished platinum filament as auxiliary electrode (platinum filament length 4cm) in pole
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains is as the second liquid for pole
It connects).At room temperature, test the cyclic voltammetry curve of the polymeric membrane, i.e., in the case where polymerizeing 0~1.6V of voltage range vs.Ag/AgC1,
To the working electrode containing polymeric membrane with rate loop voltammetric scan one week of 0.1v/s, by testing it is found that the D-A-D ' is not right
Claim structure conjugated polymer PEWT that there are more redox peaks and richer color to show when in middle condition, the material
Material is shown as BurlyWood；With the raising of voltage, which slowly becomes blue, when reaching 0.9V to voltage, is shown as bright rock grey；With
Afterwards, voltage is slowly brought up to 1.4V, is shown as mine purple.Under identical film thickness, at 1100nm, contrast is by the 31.3% of PEWE
Rise to the 48.8% of PEWT；At 650nm, contrast is increased to the 26.7% of PEWT by the 11.4% of PEWE, relative to D-A-D pairs
Claim topology convergence film PSWS, the introducing of trianilino group has significantly alterred it in visible and near infrared region optical contrast.
Embodiment 3
(1) preparation of monomer EWT
First by -9 Fluorenone (3mmol, 1.044g) of 2,7-, bis- bromo, 4- (diphenyl amido) phenyl boric acid (1.5mmol,
0.438g), the feelings that potassium carbonate (2mmol, 0.2764g) and four (three) phenyl phosphorus palladiums (0.0025mmol, 0.0311g) are protected in nitrogen
It is dissolved under condition in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and the deionized water of 2ml is added, flowed back 8
Hour, it after system is cooling, is extracted with deionized water and methylene chloride mix reagent, the organic anhydrous magnesium sulfate that is added to of gained is done
Dry, revolving mixes sample later, selects corresponding mobile phase to chromatograph column, finally obtains 2- triphenylamine -7- bromo -9- Fluorenone monomer；
Later, by 2- triphenylamine -7- bromo -9-Fluorenone monomer (3mmol, 1.503g), tributyl, (2,3- dihydro-thiophenes are simultaneously [3,4-b] -
[Isosorbide-5-Nitrae] dioxin -5- base) stannane (3mmol, 1.2963g), potassium carbonate (2mmol, 0.2764g) and bi triphenyl phosphorus dichloride
Palladium (0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20mL) and toluene (30mL), and 2ml is added
Deionized water, flow back in nitrogen atmosphere 24 hours, after system is cooling, with deionized water and methylene chloride mix reagent
Extraction, gained is organic to be added to that anhydrous magnesium sulfate is dry, and revolving mixes sample later, select corresponding mobile phase (PE: DCM=1:
1.5) column was chromatographed to get monomer (EWT).1H NMR (500MHz, DMSO) δ 8.08 (d, J=1.4Hz, 1H), 7.92 (d, J
=1.5Hz, 1H), 7.82 (dd, J=7.9,1.7Hz, 1H), 7.73 (dd, J=7.8,1.8Hz, 1H), 7.51 (d, J=3.9
Hz, 1H), 7.50 (d, J=4.1Hz, 1H), 7.39 (dd, J=3.6,1.0Hz, 1H), 7.32 (dd, J=5.1,1.0Hz, 1H),
7.11 (dd, J=5.1,3.6 Hz, 1H), 6.35 (s, 1H), 4.40-4.34 (m, 2H), 4.30-4.24 (m, 2H)) MALDI-
TOF-MS(M)(m/z)：564.1[M+H]+.
(2) preparation of polymer (PEWT) material
EWT monomer (1mmol, 0.00563g), tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in 7ml methylene chloride
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte TBAP concentration is 0.1mol/L
Mixed solution as electrolyte.Select three-electrode cell system, using indium tin electro-conductive glass (ITO) as working electrode (according to
The secondary supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, acetone, toluene, dehydrated alcohol, toluene and acetone),
Using polished platinum filament as auxiliary electrode (platinum filament length 4cm), reference electrode is done using biliquid direct type silver/silver chloride electrode
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).
Under room temperature (25 DEG C), thin polymer film is prepared using cyclic voltammetric anodic oxidation polymerization method, sets the monomer polymerization first
Starting voltage 0v, final voltage 1.6v and sweep speed 0.05v/s, and set polymerisation loop circle number and (obtain polymerization film thickness as 16
Degree is 630nm), start the working procedure of electrochemical workstation.Curve is polymerize it is found that monomer by the cyclic voltammetric of monomer
Oxidizing potential is 1.1v and 1.47v, and monomer molecule has excellent polymerization film formation ability, compared to EWE, the structures alone
EWT has more oxidation-reduction potentials.It is thin that polymerization power cut-off electrode ITO conductive glass surface deposited one layer of polymeric
Film is cleaned with methylene chloride, and the working electrode of surface deposited polymer membrane is obtained after dry, by scanning electron microscope characterization it is found that
Polymer is more loose relatively above on the surface of thin polymer film, but after 500 circulations, pattern changes smaller, explanation
Polymeric membrane is relatively stable.
(3) polymer (PEWT) electrochemical property test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in the mixed solution of 6ml methylene chloride and 4ml acetonitrile, is matched
The electrolyte solution that concentration is 0.1mol/L is made, selects three-electrode cell system, it is electric using polymeric membrane PEWT as work
Reference electricity is done using biliquid direct type silver/silver chloride electrode using polished platinum filament as auxiliary electrode (platinum filament length 4cm) in pole
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains is as the second liquid for pole
It connects).At room temperature, test the cyclic voltammetry curve of the polymeric membrane, i.e., in the case where polymerizeing 0~1.6V of voltage range vs.Ag/AgCl,
To the working electrode containing polymeric membrane with rate loop voltammetric scan one week of 0.05v/s, by testing it is found that the D-A-D ' is not right
Claim structure conjugated polymer PEWT that there are more redox peaks and richer color to show when in middle condition, the material
Material is shown as BurlyWood；With the raising of voltage, which slowly becomes blue, when reaching 0.9V to voltage, is shown as bright rock grey；With
Afterwards, voltage is slowly brought up to 1.4V, is shown as mine purple.Under identical film thickness, at 1100nm, contrast is by the 31.3% of PEWE
Rise to the 48.8% of PEWT；At 650nm, contrast is increased to the 26.7% of PEWT by the 11.4% of PEWE, relative to D-A-D pairs
Claim topology convergence film PSWS, the introducing of trianilino group has significantly alterred it in visible and near infrared region optical contrast.
Embodiment 4
(1) preparation of monomer EWT
First by -9 Fluorenone (3mmol, 1.044g) of 2,7-, bis- bromo, 4- (diphenyl amido) phenyl boric acid (1.5mmol,
0.438g), the feelings that potassium carbonate (2mmol, 0.2764g) and four (three) phenyl phosphorus palladiums (0.0025mmol, 0.0311g) are protected in nitrogen
It is dissolved under condition in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and the deionized water of 2ml is added, flowed back 8
Hour, it after system is cooling, is extracted with deionized water and methylene chloride mix reagent, the organic anhydrous magnesium sulfate that is added to of gained is done
Dry, revolving mixes sample later, selects corresponding mobile phase to chromatograph column, finally obtains 2- triphenylamine -7- bromo -9- Fluorenone monomer；
Later, by 2- triphenylamine -7- bromo -9-Fluorenone monomer (3mmol, 1.503g), tributyl, (2,3- dihydro-thiophenes are simultaneously [3,4-b] -
[Isosorbide-5-Nitrae] dioxin -5- base) stannane (3mmol, 1.2963g), potassium carbonate (2mmol, 0.2764g) and bi triphenyl phosphorus dichloride
Palladium (0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20mL) and toluene (30mL), and 2ml is added
Deionized water, flow back in nitrogen atmosphere 24 hours, after system is cooling, with deionized water and methylene chloride mix reagent
Extraction, gained is organic to be added to that anhydrous magnesium sulfate is dry, and revolving mixes sample later, select corresponding mobile phase (PE: DCM=1:
1.5) column was chromatographed to get monomer (EWT).1H NMR (500MHz, DMSO) δ 8.08 (d, J=1.4Hz, 1H), 7.92 (d, J
=1.5Hz, 1H), 7.82 (dd, J=7.9,1.7Hz, 1H), 7.73 (dd, J=7.8,1.8Hz, 1H), 7.51 (d, J=3.9
Hz, 1H), 7.50 (d, J=4.1Hz, 1H), 7.39 (dd, J=3.6,1.0Hz, 1H), 7.32 (dd, J=5.1,1.0Hz, 1H),
7.11 (dd, J=5.1,3.6 Hz, 1H), 6.35 (s, 1H), 4.40-4.34 (m, 2H), 4.30-4.24 (m, 2H)) MALDI-
TOF-MS(M)(m/z)：564.1[M+H]+.
(2) preparation of polymer (PEWT) material
By EWT monomer (1mmol, 0.00563g), lithium hexafluoro phosphate (1mmol, 0.152g) be dissolved in 7ml methylene chloride with
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte TBAP concentration is 0.1mol/L's
Mixed solution is as electrolyte.Three-electrode cell system is selected, (successively using indium tin electro-conductive glass (ITO) as working electrode
The supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, acetone, toluene, dehydrated alcohol, toluene and acetone), with
Polished platinum filament is reference electrode (Ag/ as auxiliary electrode (platinum filament length 4cm), using biliquid direct type silver/silver chloride electrode
The potassium chloride solution of AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).In room
Under warm (25 DEG C), thin polymer film is prepared using cyclic voltammetric anodic oxidation polymerization method, sets the starting of the monomer polymerization first
Voltage 0v, final voltage 1.6v and sweep speed 0.1v/s, and set polymerisation loop circle number (obtaining polymeric film thicknesses is as 16
630nm), start the working procedure of electrochemical workstation.By the cyclic voltammetric polymerization curve of monomer it is found that the oxidation of monomer
Current potential is 1.1v and 1.47v, and monomer molecule has excellent polymerization film formation ability, is had compared to EWE, structures alone EWT
There are more oxidation-reduction potentials.Polymerization power cut-off electrode ITO conductive glass surface deposited one layer of polymeric film, with two
Chloromethanes cleaning obtains the working electrode of surface deposited polymer membrane, is characterized by scanning electron microscope it is found that polymer thin after dry
Polymer is more loose relatively above on the surface of film, but by 500 circulation after, pattern variation it is smaller, illustrate polymeric membrane compared with
For stabilization.
(3) polymer (PEWT) electrochemical property test
Lithium hexafluoro phosphate (1mmol, 0.152g) is dissolved in the mixed solution of 6ml methylene chloride and 4ml acetonitrile, is configured to
Concentration is the electrolyte solution of 0.1mol/L, selects three-electrode cell system, using polymeric membrane PEWT as working electrode, with
Polished platinum filament is reference electrode (Ag/ as auxiliary electrode (platinum filament length 4cm), using biliquid direct type silver/silver chloride electrode
The potassium chloride solution of AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).In room
Under temperature, the cyclic voltammetry curve of the polymeric membrane is tested, i.e., in the case where polymerizeing 0~1.6V of voltage range vs.Ag/AgCl, to containing poly-
The working electrode of film is closed with rate loop voltammetric scan one week of 0.1v/s, by the cyclic voltammetry curve of polymeric membrane it is found that the D-
There are A-D ' dissymmetrical structure conjugated polymer PEWT more redox peaks and richer color to show when in neutrality
When state, which is shown as BurlyWood；With the raising of voltage, which slowly becomes blue, when reaching 0.9V to voltage, is shown as bright
Rock grey；Then, voltage is slowly brought up to 1.4V, is shown as mine purple.It is right at 1100nm by test it is found that under identical film thickness
The 48.8% of PEWT is risen to by the 31.3% of PEWE than degree；At 650nm, contrast is increased to PEWT by the 11.4% of PEWE
26.7%, relative to D-A-D symmetrical structure polymeric membrane PSWS, the introducing of trianilino group significantly alterred its visible and
The optical contrast of near infrared region.
Embodiment 5
(1) preparation of monomer EWT
First by -9 Fluorenone (3mmol, 1.044g) of 2,7-, bis- bromo, 4- (diphenyl amido) phenyl boric acid (1.5mmol,
0.438g), the feelings that potassium carbonate (2mmol, 0.2764g) and four (three) phenyl phosphorus palladiums (0.0025mmol, 0.0311g) are protected in nitrogen
It is dissolved under condition in the mixed solution of tetrahydrofuran (20ML) and toluene (30ML), and the deionized water of 2ml is added, flowed back 8
Hour, it after system is cooling, is extracted with deionized water and methylene chloride mix reagent, the organic anhydrous magnesium sulfate that is added to of gained is done
Dry, revolving mixes sample later, selects corresponding mobile phase to chromatograph column, finally obtains 2- triphenylamine -7- bromo -9- Fluorenone monomer；
Later, by 2- triphenylamine -7- bromo -9-Fluorenone monomer (3mmol, 1.503g), tributyl, (2,3- dihydro-thiophenes are simultaneously [3,4-b] -
[Isosorbide-5-Nitrae] dioxin -5- base) stannane (3mmol, 1.2963g), potassium carbonate (2mmol, 0.2764g) and bi triphenyl phosphorus dichloride
Palladium (0.025mmol, 0.01755g) is dissolved in the mixed solution of tetrahydrofuran (20mL) and toluene (30mL), and 2ml is added
Deionized water, flow back in nitrogen atmosphere 24 hours, after system is cooling, with deionized water and methylene chloride mix reagent
Extraction, gained is organic to be added to that anhydrous magnesium sulfate is dry, and revolving mixes sample later, select corresponding mobile phase (PE: DCM=1:
1.5) column was chromatographed to get monomer (EWT).1H NMR (500MHz, DMSO) δ 8.08 (d, J=1.4Hz, 1H), 7.92 (d, J
=1.5Hz, 1H), 7.82 (dd, J=7.9,1.7Hz, 1H), 7.73 (dd, J=7.8,1.8Hz, 1H), 7.51 (d, J=3.9
Hz, 1H), 7.50 (d, J=4.1Hz, 1H), 7.39 (dd, J=3.6,1.0Hz, 1H), 7.32 (dd, J=5.1,1.0Hz, 1H),
7.11 (dd, J=5.1,3.6 Hz, 1H), 6.35 (s, 1H), 4.40-4.34 (m, 2H), 4.30-4.24 (m, 2H)) MALDI-
TOF-MS(M)(m/z)：564.1[M+H]+.
(2) preparation of polymer (PEWT) material
EWT monomer (1mmol, 0.00563g), tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in 7ml methylene chloride
In the mixed solution of 3ml acetonitrile, it is configured to that monomer concentration is 0.005mol/L, supporting electrolyte TBAP concentration is 0.1mol/L
Mixed solution as electrolyte.Select three-electrode cell system, using indium tin electro-conductive glass (ITO) as working electrode (according to
The secondary supersound washing 15min in 0.1% sodium hydroxide solution, dehydrated alcohol, acetone, toluene, dehydrated alcohol, toluene and acetone),
Using polished platinum filament as auxiliary electrode (platinum filament length 4cm), reference electrode is done using biliquid direct type silver/silver chloride electrode
(potassium chloride solution of Ag/AgCl, 3mol/L connect as the first liquid, and the electrolyte that above-mentioned preparation obtains connects as the second liquid).
Under room temperature (25 DEG C), thin polymer film is prepared using cyclic voltammetric anodic oxidation polymerization method, sets the monomer polymerization first
Starting voltage 0v, final voltage 1.6v and sweep speed 0.1v/s, and set polymerisation loop circle number and (obtain polymeric film thicknesses as 16
For 630nm), start the working procedure of electrochemical workstation.By the cyclic voltammetry curve of monomer it is found that the oxidation electricity of monomer
Position is 1.1v and 1.47v, and monomer molecule has excellent polymerization film formation ability, and compared to EWE, structures alone EWT has
More oxidation-reduction potentials.Polymerization power cut-off electrode ITO conductive glass surface deposited one layer of polymeric film, with two
Chloromethanes cleaning obtains the working electrode of surface deposited polymer membrane after dry, by scanning electron microscope it is found that thin polymer film
Polymer is more loose relatively above on surface, but after 500 circulations, pattern variation is smaller, illustrates that polymeric membrane is more steady
It is fixed.
(3) polymer (PEWT) electrochemical property test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in the mixed solution of 12ml methylene chloride and 8ml acetonitrile,
It is configured to the electrolyte solution that concentration is 0.05mol/L, three-electrode cell system is selected, using polymeric membrane PEWT as work
Electrode does reference using biliquid direct type silver/silver chloride electrode using polished platinum filament as auxiliary electrode (platinum filament length 4cm)
(potassium chloride solution of Ag/AgCl, 3mol/L connect electrode as the first liquid, and the electrolyte that above-mentioned preparation obtains is as the second liquid
It connects).At room temperature, test the cyclic voltammetry curve of the polymeric membrane, i.e., in the case where polymerizeing 0~1.6V of voltage range vs.Ag/AgCl,
To the working electrode containing polymeric membrane with rate loop voltammetric scan one week of 0.1v/s, by testing it is found that the D-A-D ' is not right
Claim structure conjugated polymer PEWT that there are more redox peaks and richer color to show when in middle condition, the material
Material is shown as BurlyWood；With the raising of voltage, which slowly becomes blue, when reaching 0.9V to voltage, is shown as bright rock grey；With
Afterwards, voltage is slowly brought up to 1.4V, is shown as mine purple.Under identical film thickness, at 1100nm, contrast is by the 31.3% of PEWE
Rise to the 48.8% of PEWT；At 650nm, contrast is increased to the 26.7% of PEWT by the 11.4% of PEWE, relative to D-A-D pairs
Claim topology convergence film PSWS, the introducing of trianilino group has significantly alterred it in visible and near infrared region optical contrast.
Claims (10)
1. a kind of D-A-D ' unsymmetric structure polymeric membrane PEWT, it is characterised in that：D-A-D ' the unsymmetric structure polymeric membrane
PEWT is specifically prepared as follows：
(1) -9 Fluorenone of 2,7-, bis- bromo shown in formula 1 is mixed with 4- (diphenyl amido) phenyl boric acid, four (three) phenyl phosphorus palladiums,
It under the action of alkaline matter A, is dissolved in organic solvent A in the case where nitrogen is protected, reacts 8-12 hours at a reflux temperature,
Reaction mixture B is obtained, it is post-treated to obtain product 2- triphenylamine -7- bromo -9-Fluorenone shown in formula 2；Shown in the formula 1
The ratio between amount of substance of -9 Fluorenone of bis- bromo of 2,7- and 4- (diphenyl amido) phenyl boric acid, four (three) phenyl phosphorus palladiums is 1：0.5~
1：0.001~0.005；The alkaline matter A is added in form of an aqueous solutions, and the additional amount of the water to dissolve alkalinity just
Subject to substance A；The additional amount of the alkaline matter A is calculated as 2~4mol/L with the volume of the organic solvent A；Described
The additional amount of organic solvent A is calculated as 10~100mL/ with the amount of the substance of -9 Fluorenone of bis- bromo of 2,7- shown in the formula 1
mmol；
(2) by 2- triphenylamine -7- bromo -9-Fluorenone shown in formula 2 and tributyl (2,3- dihydro-thiophene simultaneously [1,4] [3,4-b] -
Dioxin -5- base) stannane, bi triphenyl phosphorus palladium chloride, under the action of alkaline matter B, nitrogen protect in the case where be dissolved in
In organic solvent B, reacts 24-36 hours at a reflux temperature, obtain reaction mixture C, it is post-treated to obtain D-A- shown in formula 3
D ' unsymmetric structure monomer EWT；2- triphenylamine -7- bromo-the 9-Fluorenone and tributyl (2,3- dihydro-thiophene simultaneously [3,4-
B]-[1,4] dioxin -5- base) stannane, bi triphenyl phosphorus palladium chloride the ratio between the amount of substance be 1：1~2：0.001~
0.005；The alkaline matter B is added in form of an aqueous solutions, and the additional amount of the water is to dissolve alkaline matter B just
It is quasi-；The additional amount of the alkaline matter B is calculated as 2~4mol/L with the volume of the organic solvent B；The organic solvent
The additional amount of B is calculated as 10~100mL/mmol with the amount of 2- triphenylamine -7- bromo -9-Fluorenone substance shown in the formula 2；
(3) D-A-D ' unsymmetric structure monomer EWT obtained by step (3), support electrolyte are dissolved in electroanalysis solvent and are electrolysed
Liquid, in three-electrode cell, using cyclic voltammetric anodic oxidation polymerization method, in polymerization voltage range in 0~1.6V vs.Ag/
AgCl carries out deposition reaction, after fully reacting, obtains depositing on the working electrode (s under conditions of polymerisation loop circle number is 2~32
Thin polymer film, through organic solvent cleaning, be dried to obtain thin polymer film PEWT shown in formula 4；The support electrolyte
For ammonium salt, lithium salts or 1- butyl -3- methyl imidazolium tetrafluoroborate；It is 1 that the electrolytic cell solvent, which is volume ratio,：0.1~10
Acetonitrile and methylene chloride mixed solvent；D-A-D ' unsymmetric structure monomer EWT shown in the formula 3 or support electrolyte
Additional amount come by the volume of the electroanalysis solvent in terms of, D-A-D ' unsymmetric structure monomer EWT shown in the formula 3
Initial final concentration of 0.1~10mmol/L electroanalysis solvent, initial final concentration of 0.01~1mol/L of the supporting electrolyte
Electroanalysis solvent；
The three-electrode system is made of electrolytic cell, working electrode, auxiliary electrode and reference electrode, and the working electrode is
Perhaps the PET conductive film electrode auxiliary electrode is platinum electrode or platinum carbon electrode, institute by indium tin oxide-coated glass, FTO
It with the potassium chloride solution of 3mol/L is that the first liquid connects that the reference electrode stated, which is Ag/AgCl, with the electrolyte for the second liquid
It connects；
2. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (1)
Alkaline matter A is sodium carbonate, sodium bicarbonate or potassium carbonate.
3. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (1)
Organic solvent A is the mixed solvent that tetrahydrofuran mixes in any proportion with toluene.
4. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (2)
Alkaline matter B is sodium carbonate, sodium bicarbonate or potassium carbonate.
5. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (2)
Organic solvent B is the mixed solvent that tetrahydrofuran mixes in any proportion with toluene.
6. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：In step (2), gained is anti-
The last handling process for answering mixed liquor C is：After reaction, deionized water and methylene chloride are added into gained reaction mixture C
Mix reagent extracted, it is simultaneously dry with anhydrous magnesium sulfate to merge organic phase, revolving mixes sample, with volume ratio for 1：0.5-2.5
Petroleum ether and the mixed solvent of methylene chloride be that mobile phase composition through chromatography obtains D-A-D ' unsymmetrical knot shown in formula 3
Structure monomer EWT.
7. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (3)
Ammonium salt is tetrabutylammonium perchlorate or tetrabutyl ammonium hexafluorophosphate.
8. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：It is described in step (3)
Lithium salts is lithium hexafluoro phosphate, LiBF4 or trifluoromethyl sulfonic acid lithium.
9. D-A-D ' unsymmetric structure polymeric membrane PEWT as claimed in claim 1, it is characterised in that：In step (3), the use
It is volume ratio in the organic solvent of cleaning is 1:0.1~10 acetonitrile and methylene chloride mixed solvent.
10. a kind of D-A-D ' unsymmetric structure polymeric membrane PEWT as described in claim 1 is applied to prepare electrochromic device.
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| US20070009761A1 (en) * | 2005-02-28 | 2007-01-11 | Sanyo Electric Co., Ltd. | Hole transport material for organic electroluminescence devices and organic electroluminescence device using the same |
| WO2013008951A1 (en) * | 2011-07-13 | 2013-01-17 | National Institute For Materials Science | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell |
| CN103923106A (en) * | 2014-04-29 | 2014-07-16 | 常州大学 | Low-energy-gap and broad-absorption conjugated polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070009761A1 (en) * | 2005-02-28 | 2007-01-11 | Sanyo Electric Co., Ltd. | Hole transport material for organic electroluminescence devices and organic electroluminescence device using the same |
| WO2013008951A1 (en) * | 2011-07-13 | 2013-01-17 | National Institute For Materials Science | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell |
| CN103923106A (en) * | 2014-04-29 | 2014-07-16 | 常州大学 | Low-energy-gap and broad-absorption conjugated polymer and preparation method thereof |
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| CN113388104A (en) * | 2021-07-02 | 2021-09-14 | 黑龙江大学 | Triarylamine polyamide containing fluorenyl directly bonded with triphenylamine, and preparation method and application thereof |
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